Two topologically comparable complexes, [Ag-6(CF3CO2)(3)(L1-Me)(3)(SCH3)(3)](infinity) (1) and [Ag-6(CF3CF2CO2)(3)(L1-Me)(2)(SCH3)(3)(H2O)](infinity) (2), were prepared and characterized by single-crystal diffractometry. The structures consist of Ag12S6 clusters linked by bis(methylthio)methane ligands, L1-Me, thus forming 1D coordination polymers. The 12 Ag atoms of the cluster are situated at the corners of a distorted cuboctahedron. The sulfur atoms of the six mu(4)-SCH3 entities occupy a position similar to 0.8 angstrom above the center of each of the square faces of the polyhedron. The cleavage of the C-S bond of some of the ligands occurs during the syntheses, producing the -SCH3 anions. The coordination of the silver atoms varies from 5 to 7. The Ag center dot center dot center dot Ag contacts range from 2.9250(5) to 3.3615(6) angstrom and from 2.961(1) to 3.380(1) angstrom for 1 and 2, respectively. A polymeric ribbon is obtained when four ligands link a given cluster to two others. The chains of 1, held only by van der Waals forces, pack in a hexagonal manner. The two water molecules in 2 (Ag-OH2 = 2.385(7) angstrom) are coordinated to silver atoms of the cluster. They are also strongly hydrogen bonded to the oxygen atoms of two pentafluoropropionate groups, one within the cluster (O center dot center dot center dot O = 2.741(1) angstrom), the other in an adjacent chain (O center dot center dot center dot O = 2.818(1) angstrom). The chains, thus H bonded to one another, generate a 2D coordination network.